US5162401A - Unsaturated polyester resin compositions containing compatible compounds - Google Patents

Unsaturated polyester resin compositions containing compatible compounds Download PDF

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US5162401A
US5162401A US07/517,775 US51777590A US5162401A US 5162401 A US5162401 A US 5162401A US 51777590 A US51777590 A US 51777590A US 5162401 A US5162401 A US 5162401A
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molecular weight
composition
compatible component
polyethoxylated
compatible
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US07/517,775
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Louis R. Ross
Paul R. Krumlauf
Edward L. Wilson
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AOC LLC
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Owens Corning Fiberglas Corp
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Priority claimed from US07/428,548 external-priority patent/US5089544A/en
Application filed by Owens Corning Fiberglas Corp filed Critical Owens Corning Fiberglas Corp
Priority to US07/517,775 priority Critical patent/US5162401A/en
Priority to DE69031800T priority patent/DE69031800D1/en
Priority to AU67300/90A priority patent/AU6730090A/en
Priority to BR909006979A priority patent/BR9006979A/en
Priority to ES90916979T priority patent/ES2113863T3/en
Priority to PCT/US1990/005541 priority patent/WO1991006604A1/en
Priority to EP90916979A priority patent/EP0451258B1/en
Priority to JP2515512A priority patent/JPH04502645A/en
Priority to CA002026636A priority patent/CA2026636A1/en
Priority to KR1019910700668A priority patent/KR920701357A/en
Priority to DK90916979T priority patent/DK0451258T3/en
Priority to CN90108700A priority patent/CN1030713C/en
Assigned to OWENS-CORNING FIBERGLAS CORPORATION A CORPORATION OF DELAWARE reassignment OWENS-CORNING FIBERGLAS CORPORATION A CORPORATION OF DELAWARE ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: KRUMLAUF, PAUL R., ROSS, LOUIS R., WILSON, EDWARD L.
Priority to NO91912465A priority patent/NO912465L/en
Priority to FI913164A priority patent/FI913164A0/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/06—Unsaturated polyesters

Definitions

  • the present invention provides unsaturated polyester resin compositions that contain one or more unsaturated polyesters, ethylenically unsaturated monomers that copolymerize with the unsaturated polymer, thermoplastic low-profile additives and compatible compounds.
  • Unsaturated polyester resin compositions are finding increased use in the automotive industry as sheet molding compound (SMC) formulations from which component parts especially body panels can be molded.
  • the unsaturated polyester resin compositions contain, in addition to the unsaturated polyesters and monomer components, so-called "low-profile” additive components which are thermoplastic polymers that act to prevent undesirable shrinkage as the composition is being molded into a thermoset article.
  • Low-profile additives are added to unsaturated polyester resin compositions in order to obtain a composition which can be used in a sheet molding formulation and molded into thermoset articles.
  • the surfaces of the molded articles truly reflect the surface characteristics of the mold.
  • Two types of low-profile systems are commonly used commercially, one-pack and two-pack.
  • one-pack systems the unsaturated polyester, monomer and low-profile additive components are mutually compatible, i.e., no gross separation occurs when a mixture of the components is allowed to stand.
  • two-pack systems form distinct phases if the components are allowed to stand after being mixed. As such, the components need to be mixed immediately prior to use. In both systems, phenomena occur that allow these resins to microscopically compensate for shrinkage.
  • the low-profile resins It is the ability of the low-profile resins to compensate for shrinkage that leads to the usefulness of these resins.
  • This shrinkage compensation is largely a result of a micro-phase separation that occurs in these unsaturated polyester resin systems.
  • the micro-phase separation occurs during the cure phase for both the one-pack and two-pack systems.
  • Prior to cure the low-profile additive is at least partly soluble in the polyester/monomer solution. As the polyester/monomer mixture crosslinks, the low-profile thermoplastic additive and copolymer (of polyester and monomer) become increasingly less compatible and a two-phase (domain-matrix) type morphology results.
  • This micro-phase separation leads to the formation of a porous structure as the opposing internal stresses of thermal expansion and polymerization shrinkage occur.
  • the sheet molding compound formulations typically contain other ingredients including, for example, chemical thickeners.
  • a chemical thickener such as an alkaline material (for example, magnesium oxide or magnesium hydroxide) is added to an uncured polyester along with fillers, glass fiber, and other standard materials.
  • the alkaline material interacts with the residual acidity in the polyester and, usually, the low-profile additive to increase the viscosity of the composition. This process is referred to as maturation and usually takes several days. If two-pack resin systems are used, care has to be taken to avoid gross phase separation. After the maturation process is complete, the thickened formulations are handlable and can easily be placed into compression molds either by hand or by machine.
  • Low-profile resins have been described that contain unsaturated polyester resins, thermoplastic low-profile additives, and a polymerizable monomer, usually styrene. In addition to these components other materials have been added to low-profile systems to improve specific properties.
  • phase stabilizing agent that comprise a select group of compounds from three classes: fatty acids, dimer acids are polyester polyols.
  • fatty acids dimer acids are polyester polyols.
  • the phase stabilizing agent reduces the gross separation that occurs during the maturation process.
  • the resin compositions described by Iseler et al. are two-pack systems that formerly phase-separated during maturation prior to the addition of the phase stabilizers.
  • the Ochsenbein et al. U.S. Pat. No. 4,473,544 describes an anti-shrink additive with a tri- or tetrafunctional polyether condensation product of propylene oxide on a triol or tetrol wherein the condensation product is acidified in such a manner that it possesses at least one terminal acidic functional group per elementary molecule. This material is used as a low-profile additive.
  • the Atkins U.S. Pat. No. 4,555,534 describes low-shrink pigmentable unsaturated polyester resins which comprises a polyester resin comprising the reaction product of an olefinically unsaturated dicarboxylic acid or anhydride and a polyol, an olefinically unsaturated monomer, a thickening agent, a pigment, a carboxylated vinyl acetate polymer low-profile additive, and a surface active compound.
  • the Atkins '534 patent describes low-shrink resins having improved uniformity of pigmentation in internally pigmented thickened polyester molding compositions. These pigmentable resin systems are low-shrink, and now low-profile. The surface quality of these pigmentable systems is considerably inferior to surfaces required for automotive appearance applications.
  • the present invention provides low-profile resin compositions having improved surface smoothness which are useful for compression or injection molding into useful articles.
  • the invention comprises an improved sheet molding composition that includes a four component resinous system comprising:
  • an unsaturated polyester comprising a poly condensation product of one or more dihydric alcohols and one or more ethylenically unsaturated polycarboxylic acids
  • thermoplastic polymers which cause phase separation and porosity during the curing reaction
  • the four component resinous system imparts improved surface smoothness when used with other known, conventional ingredients for low-profile resin systems used in making sheet molding compositions.
  • the present invention relates to the discovery of the use in a low-profile system of components which remain compatible with a curing unsaturated polyester resin and monomer.
  • these compatible components are included in combination with low-profile additives and used in sheet molding compositions, articles with very smooth surfaces may be molded. Additionally, the flow of the sheet molding composition during the molding process is improved to the point that rapidly curing formulations may be composed. As a result, the molding time is drastically reduced.
  • the unsaturated polyester component of the four component resinous system comprises the polycondensation reaction product of one or more dihydric alcohols and one or more ethylenically unsaturated polycarboxylic acids.
  • polycarboxylic acid is generally meant the polycarboxylic or dicarboxylic acids or anhydrides, polycarboxylic or dicarboxylic acid halides, and polycarboxylic or dicarboxylic esters.
  • Suitable unsaturated polycarboxylic acids, and the corresponding anhydrides and acid halides that contain polymerizable carbon-to-carbon double bonds may include maleic anhydride, maleic acid, and fumaric acid.
  • a minor proportion of the unsaturated acid, up to about forty mole percent, may be replaced by dicarboxylic or polycarboxylic acid that does not contain a polymerizable carbon-to-carbon bond.
  • dicarboxylic or polycarboxylic acid that does not contain a polymerizable carbon-to-carbon bond. Examples of which include O-phthalic, isophthalic, terephthalic, succinic, adipic, sebacic, methyl-succinic, and the like.
  • Dihydric alcohols that are useful in preparing the polyesters include 1,2-propane diol (hereinafter referred to as propylene glycol), dipropylene glycol, diethylene glyco, 1,3-butanediol, ethylene glycol, glycerol, and the like.
  • polyesters examples include the polycondensation products of (1) propylene glycol and maleic and/or fumaric acids; (2) 1,3-butanediol and maleic and/or fumaric acids; (3-combinations of ethylene and propylene glycols (approximately 50 mole percent or less of ethylene glycol) and maleic and/or fumaric acid; (4) propylene glycol, maleic and/or fumaric acids and dicyclopentadiene reacted with water.
  • dicyclopentadiene modified unsaturated polyester reins as described in the Pratt et al. U.S. Pat. No. 3,883,612.
  • polyesters which have been condensed to acid numbers of less than 100 are generally useful, but acid numbers less than 70 are preferred.
  • the molecular weight of the polymerizable unsaturated polyester may vary over a considerable range, but ordinarily those polyesters useful in the practice of the present invention have a molecular weight ranging from 300 to 5000, and more preferably, from about 500 to 5000.
  • the unsaturated polyester is present in amounts ranging from about 20 to 45 percent, by weight, based on the total four component resinous system comprising the unsaturated polyester, the low-profile additive, monomer and compatible component. Especially preferred concentrations of the unsaturated polyester are in the 28 to 35 percent, by weight, range.
  • Low-profile additives are materials that when mixed in an unsaturated polyester and cured, result in a multiphase system. If the low-profile additive and the unsaturated polyester are compatible (from the standpoint that a gross phase separation does not take place) before cure, the system is known as a one-pack. Those mixtures which tend to separate into two or more layers on standing are known as a two-pack resin systems. This does, however, necessitate mixing immediately before use.
  • Some polymers that are useful as low-profile additives include homopolymers and compolymers of acrylic and methacrylic acid esters, cellulose acetate butyrate, vinyl acetate homopolymers and copolymers, polyethylanes prepared from polyisocyanates, preferably diisocyanates, and polyether polyols, numerous saturated polyesters, polycaprolactone, styrenebutadiene copolymers, some modified celluloses, and certain alkyl oxide polymers.
  • the above list of low-profile additives is not intended to list all low-profile additives but rather to show examples of materials which have been used to cause the multiphase morphology present in low profile resins.
  • the thermoplastic additive is present in amounts ranging from 5 to 30 percent, by weight, based on the total four component resinous system. Especially preferred concentrations of thermoplastic additive are in the 7 to 20 percent, by weight range.
  • the monomer component of the resinous system comprises materials that copolymerize with the unsaturated polyester.
  • the olefinically unsaturated monomer that is copolymerizible with the unsaturated polyester is most generally styrene, however, methyl-styrene is also useful.
  • the monomer is present in amounts ranging from 25 to 65 percent, by weight, based on the total four component resinous system. Especially preferred concentrations of monomer are in the 35 to 50 percent, by weight range.
  • one or more components are added which are compatible with the unsaturated polyester and monomer during the cure phase. That is, they do not act as low-profile additives. They do not cause a microphase separation during cure.
  • these compatible components give the added benefits of surface smoothness and better flowability, when compared with low-profile resin compositions without the compatible components.
  • the compatible component is present in amounts ranging from 0.5 to 15 percent, by weight, based on the total four component resinous sytem. Especially preferred concentrations of the compatible components are in the 1 to 8 percent, by weight range.
  • the compatible components of the present invention contain one or more oxyethane units, i.e., ##STR1## wherein R 1 , R 2 , R 3 , and R 4 , are selected from the group consisting of hydrogen, cycloalkyl, lower alkyl, phenyl, phenyl substituted by halogen, lower alkyl, acryl, or lower alkoxy; R 1 , R 2 , R 3 , and R 4 may be the same or different; and a is an integer between about 1 and 200, and in some embodiments a is less than 100 and in certain embodiment a is less than 70.
  • cycloalkyl generally contain from 1 to 50 carbons, as is well understood by those skilled in the art.
  • a compatible component is a compound containing one of more polyoxyethane substituents for the Formula I above wherein R 1 , R 2 , R 3 and R 4 are selected from the group consisting of H and lower alkyl; R 1 , R 2 , R 3 and R 4 may be the same or different; and, a is an integer between 1 and about 200, and in certain embodiments between 1 and about 70.
  • the molecular weight of the compatible component is less than about 4000, the weight percent of the oxyethane unit described above is greater than or equal to 20, and the other atoms total is less than 240.
  • the molecular weight of the compatible compound is such that the compatible component remains compatible with the curing unsaturated polyester and monomer.
  • Compatibility generally means that the combination of unsaturated polyester and low-profile additive do not cause the microporous phase separation widely accepted as necessary for the low-profile phenomenon.
  • Low-profile additive components by definition, are incompatible with the curing unsaturated polyester and monomer, and cause phase separation.
  • compatible components that contain polyoxyethane substituents are polymers such as a polyalkylene oxide which has a molecular weight of between about 200-5000.
  • the molecular weight of the polyalkylene oxide polymer is such that the compatible component remains compatible with the curing unsaturated polyester and monomer.
  • the polyalkylene oxide polymer is incompatible with the curing unsaturated polyester and monomer.
  • the polyalkylene oxide polymer acts like a low-profile additive component, which by definition, is incompatible with the curing unsaturated polyester and monomer.
  • Specific examples of polyalkylene oxide polymers useful as compatible components include polypropylene oxide having a molecular weight between about 200-1000 and polyethylene oxide having a molecular weight between about 200-5000.
  • compatible components containing one or more polyoxyethane substituents are polyalkoxylated alkyl phenols such as polypropoxylated nonyl phenols, polyethoxylated nonyl phenols, polypropoxylated octyl phenols, polyethoxyated octyl phenols, and the like.
  • R 5 is alkyl and R 1 , R 2 , R 3 , R 4 and R 6 are selected from the group consisting of hydrogen, cycloalkyl, lower alkyl, phenyl, phenyl substituted by halogen, lower alkyl, acyl, or lower alkoxy; R 1 , R 2 , R 3 , R 4 , R 5 and R 6 may be the same or different; and a is an integer between 1 and about 200.
  • R 1 , R 2 , R 3 , R 4 are selected from the group consisting of hydrogen, cycloalkyl, lower alkyl, phenyl, phenyl substituted by halogen, lower alkyl, acryl, or lower alkoxy;
  • R 5 , and R 6 are selected from the group consisting of hydrogen substituted benzyl, cycloalkyl, lower alkyl, phenyl, phenyl substituted by halogen, lower alkyl, acyl, or lower alkoxy,
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 maybe the same or different, and a is an integer between 1 and about 200.
  • R 5 CH 3
  • R 6 is OCOCH 3
  • a 2. This is dipropylene glycol monomethyl ether acetate.
  • This is dipropylene glycol monomethyl ether.
  • This is tripropylene glycol monomethyl ether.
  • compatible components of the present invention include ethoxylated amines, such as for example, ##STR4## or mixtures of these wherein Z is the oxyethane unit, formula I above, R 7 and R 8 are hydrogen or a moiety containing between one and 25 carbon atoms, which may contain oxygen atoms, nitrogen atoms.
  • a specific type of amine is ##STR5## wherein R 1 , R 2 , R 3 , R 4 , and R 7 are selected from the group consisting of hydrogen, cycloalkyl, lower alkyl, phenyl, phenyl substituted by halogen, lower alkyl, acyl, or lower alkoxy, R 5 , and R 6 are selected from the group consisting of hydrogen, or hydrocarbon chains containing 8-22 carbons, or cycloalkyl, lower alkyl phenyl, phenyl substituted by halogen, lower alkyl, acyl, or lower alkoxy, and a is an integer between 1 and about 200, and R 1 , R 2 , R 3 , and R 7 , may be the same or different, and R 5 , and R 6 , may be the same or different.
  • the compatible components of the present invention include monosaccharides that are partially esterified with carboxylic acid, and one or more of the remaining hydroxyls are ethoylated.
  • R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 must be comprise the oxyethane group depicted in Formula I and the remainder must comprise hydrogen or ##STR8## (wherein R 7 is cycloalkyl, alkyl up to 22 carbons, lower alkyl, phenyl, phenyl substituted by halogen, lower alkyl, or phenyl).
  • One example of such a monsaccharide comprises an ethoxylated sorbitan monooleate with about 5 ethylene oxide units.
  • An additional example is an ethoxylated sorbitan monooleate with about 20 ethylene oxide units.
  • the four component resinous system of this invention is suitable for mixing with other ingredients in order to form a sheet molding composition.
  • the four component resinous system is suitable for mixing with chemical thickeners which are physically mixed into the resin emulsion.
  • the chemical thickeners generally include metal oxides, hydroxides and alkoxides of Group II, III or IV from the Periodic Table. Calcium oxide and magnesium oxide or the respective hydroxides are most often employed with four component resin compositions of the present invention.
  • the thickener is present in amounts ranging from about 0.5 to about 6 parts, by weight, based on the four component resinous system.
  • the thickener is generally suspended in a carrier resin, as is known in the art.
  • the carrier material comprises a composition which does not react with the thickener such as, for example, polymethylmethacrylate, polyvinylacetate, saturated or unsaturated polyesters, and similar materials well-known in the art.
  • the carrier resin is present in amounts ranging from about 0.5 to about 8 parts, by weight based on one hundred parts of the four component resinous system.
  • Table II illustrates the preferred ranged for the four component mixture described in this invention.
  • Catalysts are incorporated in small amounts into thermosetting polyester resins containing ethylenically unsaturated monomer to aid in curing or cross-linking the unsaturated polyester with the monomer.
  • Such catalysts are well known and may be similarly utilized in this invention to aid in curing the unsaturated polyester and monomer mixed with the low-profile thermoplastic polymer.
  • Typical catalysts include organic peroxide and peracids such as tertiary butyl perbenzoate, tertiary butyl peroctoate, benzoyl peroxide and the like.
  • the amounts of catalysts may be varied with the molding process and similarly varied with the level and types of inhibitors utilized, in a manner well known in the art. In preferred embodiments of the catalyst is present in amounts ranging from about 0.5 to about 2.5 parts, by weight, based on one hundred parts of the four component resinous system.
  • Curing of the composition is carried out under heat and pressure typically, in closed, preferably positive pressure type molds. Mold release agents may be added to the compositions to perform their normal function, as is well understood in the art. In preferred embodiments, the mold release agents are present in amounts ranging from about 0.5 to about 6.0 parts, by weight, based on one hundred parts of the four component resin system.
  • Fibers, fillers and pigments normally added to resin compositions can be likewise used in formulating the sheet molding composition of this invention.
  • Reinforcing fibers or fibrous reinforcement is taken to mean glass fibers in one form or another, such as glass fabrics, chopped glass strands, chopped or continuous strand glass fiber mat; however, the terms also include reinforcing agents which may also be used if desired, for example, asbestos, cotton, synthetic organic fibers and metals.
  • Fillers, usually inert, and inorganic material useful with the compositions of the present invention include, for example, clay, talc, calcium carbonate, silica, calcium silicate, and the like. In preferred embodiments the fillers are present in amounts ranging from about 165 to about 250 parts, by weight, based on one hundred parts of the four component resinous system.
  • pigments examples include carbon black, iron oxide, titanium dioxide, and the like, as well as organic pigments.
  • the pigments are present in amounts ranging from about 0 to about 4 parts, by weight, based on one hundred parts of the four component resinous system.
  • the preparation of the sheet molding composition is generally carried out by blending together a first portion comprising the unsaturated polyester, the low-profile additive, the monomer, the compatible component, and such additives as a catalyst, mold release agent and fillers.
  • the second portion (generally known as the B-side formulation) comprises the thickening agent and a carrier resin therefor, and such additives as pigments and mold release agents.
  • an additional or secondary monomer is added to the B-side formulation in which the thickener is suspended.
  • the additional monomer comprises vinyl toluene or styrene.
  • the additional monomer is present in amounts ranging from about 1 to about 8 parts, by weight, based on one hundred parts of the four component resinous system.
  • the sheet molding composition of the present invention can be prepared by mixing the components in a suitable apparatus of temperatures which are conventional and known to those skilled in the art. Once the sheet molding composition is formulated, the composition can be molded into thermoset articles having a desired shape. The actual molding cycle will, of course, depend upon the exact composition being molded. In preferred embodiments suitable molding cycles are conducted at temperatures ranging from about 250°-350° F. for periods of time ranging from about 1/3 to about 5 minutes.
  • the unsaturated polyester comprises maleic anhydride and propylene glycol
  • the low-profile additive comprises a saturated polyester made from ethylene glycol and propylene glycol and adipic acid
  • the monomer comprises styrene
  • the compatible components are listed in Table I
  • the catalyst comprises tertiary butyl perbenzoate
  • the release agent comprises calcium stearate and zinc stearate
  • the filler comprises calcium carbonate
  • the thickener comprises magnesium hydroxide
  • the carrier comprising polymethylmethacrylate
  • the pigment comprises a carbon black pigment suspension
  • the secondary monomer comprises vinyl toluene.
  • Compression molded panels were made with each formulation with 27 percent, by weight, of 1" chopped glass fibers.
  • LORIA® registered trademark of the Ashland Chemical Co.
  • the panels gave the LORIA® number as listed in Table I below as compared to the same formulation but without any compatible component, which gave a number of 80-90.
  • the additives listed in Table I below contain the oxyethylene unit, as described in this invention.
  • the compatible components especially useful in the four component resinous system have a surface smoothness value within the ranges set forth in Table I below. In preferred embodiments, it is contemplated that the surface smoothness values of the four component resinous systems containing compatible components, be about 50 or less, as measured using a LORIA® surface smoothness index instrument.
  • sheet molding compositions of the above formulations have shown unexpected improvements in surface aesthetics and mold fillout. These improvements are especially significant for use in sheet molding compound (SMC). Moreover, increasingly thinner automobile parts are able to be molded with smoother surfaces than by any known systems.
  • SMC sheet molding compound

Abstract

A sheet molding composition is disclosed which includes a four component resinous system which comprises (a) an unsaturated polyester comprising a polycondensation product of one or more dihydric alcohols and one or more ethylenically unsaturated polycarboxylic acids; (b) one or more low-profile additives which are thermoplastic polymers which cause phase separation and porosity during the curing reaction; (c) one or more olefinically unsaturated monomers which copolymerize with the unsaturated polyester; and, (d) one or more compatible components comprising at least one compound containing one or more polyoxyethane substituents. The compatible component remains compatible when the polyester and monomer cure and imparts improved surface characteristics when added to low-profile resin systems.

Description

This is a continuation-in-part of Ser. No. 07/428,548 filed Oct. 30, 1989, now U.S. Pat. No. 5,089,544.
BACKGROUND OF THE INVENTION
The present invention provides unsaturated polyester resin compositions that contain one or more unsaturated polyesters, ethylenically unsaturated monomers that copolymerize with the unsaturated polymer, thermoplastic low-profile additives and compatible compounds.
Unsaturated polyester resin compositions are finding increased use in the automotive industry as sheet molding compound (SMC) formulations from which component parts especially body panels can be molded. The unsaturated polyester resin compositions contain, in addition to the unsaturated polyesters and monomer components, so-called "low-profile" additive components which are thermoplastic polymers that act to prevent undesirable shrinkage as the composition is being molded into a thermoset article. Low-profile additives are added to unsaturated polyester resin compositions in order to obtain a composition which can be used in a sheet molding formulation and molded into thermoset articles. The surfaces of the molded articles truly reflect the surface characteristics of the mold.
Two types of low-profile systems are commonly used commercially, one-pack and two-pack. In one-pack systems, the unsaturated polyester, monomer and low-profile additive components are mutually compatible, i.e., no gross separation occurs when a mixture of the components is allowed to stand. In contrast, two-pack systems form distinct phases if the components are allowed to stand after being mixed. As such, the components need to be mixed immediately prior to use. In both systems, phenomena occur that allow these resins to microscopically compensate for shrinkage.
It is the ability of the low-profile resins to compensate for shrinkage that leads to the usefulness of these resins. This shrinkage compensation is largely a result of a micro-phase separation that occurs in these unsaturated polyester resin systems. The micro-phase separation occurs during the cure phase for both the one-pack and two-pack systems. Prior to cure the low-profile additive is at least partly soluble in the polyester/monomer solution. As the polyester/monomer mixture crosslinks, the low-profile thermoplastic additive and copolymer (of polyester and monomer) become increasingly less compatible and a two-phase (domain-matrix) type morphology results. This micro-phase separation leads to the formation of a porous structure as the opposing internal stresses of thermal expansion and polymerization shrinkage occur. In many unsaturated polyester resin compositions the porous structure is a result of microfracturing of the curing resins which gives rise to void formation. Other unsaturated polyester resins have been developed which have essentially zero shrinkage and which, in fact, expand upon curing.
In addition to unsaturated polyester resins, the sheet molding compound formulations typically contain other ingredients including, for example, chemical thickeners. In such formations, a chemical thickener such as an alkaline material (for example, magnesium oxide or magnesium hydroxide) is added to an uncured polyester along with fillers, glass fiber, and other standard materials. The alkaline material interacts with the residual acidity in the polyester and, usually, the low-profile additive to increase the viscosity of the composition. This process is referred to as maturation and usually takes several days. If two-pack resin systems are used, care has to be taken to avoid gross phase separation. After the maturation process is complete, the thickened formulations are handlable and can easily be placed into compression molds either by hand or by machine.
Although the use of low-profile additives does effect some degree of improvement in the anti-shrinkage characteristics of the unsaturated polyester compositions, it has now been found that significant improvements in surface smoothness and processing characteristics can be achieved by adding a component which remains compatible during the curing of the unsaturated polyester and monomer.
PRIOR ART
Low-profile resins have been described that contain unsaturated polyester resins, thermoplastic low-profile additives, and a polymerizable monomer, usually styrene. In addition to these components other materials have been added to low-profile systems to improve specific properties.
The Iseler, et al. U.S. Pat. No. 4,622,354 describes "phase stabilizing agent" that comprise a select group of compounds from three classes: fatty acids, dimer acids are polyester polyols. When used in an SMC formulation where the thermoplastic low-profile additive is polymethylmethacrylate and a urethane propolymer is included, the phase stabilizing agent reduces the gross separation that occurs during the maturation process. The resin compositions described by Iseler et al. are two-pack systems that formerly phase-separated during maturation prior to the addition of the phase stabilizers.
The Ochsenbein et al. U.S. Pat. No. 4,473,544 describes an anti-shrink additive with a tri- or tetrafunctional polyether condensation product of propylene oxide on a triol or tetrol wherein the condensation product is acidified in such a manner that it possesses at least one terminal acidic functional group per elementary molecule. This material is used as a low-profile additive.
The Atkins U.S. Pat. No. 4,555,534 describes low-shrink pigmentable unsaturated polyester resins which comprises a polyester resin comprising the reaction product of an olefinically unsaturated dicarboxylic acid or anhydride and a polyol, an olefinically unsaturated monomer, a thickening agent, a pigment, a carboxylated vinyl acetate polymer low-profile additive, and a surface active compound. The Atkins '534 patent describes low-shrink resins having improved uniformity of pigmentation in internally pigmented thickened polyester molding compositions. These pigmentable resin systems are low-shrink, and now low-profile. The surface quality of these pigmentable systems is considerably inferior to surfaces required for automotive appearance applications.
Although the use of low-profile additives and thickening agents, as described, do effect some degree of improvement in the antishrinkage and surface smoothness characteristics of the unsaturated polyester compositions, it is still not possible to achieve the degree of surface smoothness required of today's thermoset molded articles.
SUMMARY OF THE INVENTION
The present invention provides low-profile resin compositions having improved surface smoothness which are useful for compression or injection molding into useful articles. In one aspect, the invention comprises an improved sheet molding composition that includes a four component resinous system comprising:
(a) an unsaturated polyester comprising a poly condensation product of one or more dihydric alcohols and one or more ethylenically unsaturated polycarboxylic acids;
(b) one or more low-profile additives comprising thermoplastic polymers which cause phase separation and porosity during the curing reaction;
(c) one or more olefinically unsaturated monomers which copolymerize with the unsaturated polyester; and,
(d) one or more components that remain compatible during the curing of the polyester and monomer.
The four component resinous system imparts improved surface smoothness when used with other known, conventional ingredients for low-profile resin systems used in making sheet molding compositions.
DESCRIPTION OF INVENTION
The present invention relates to the discovery of the use in a low-profile system of components which remain compatible with a curing unsaturated polyester resin and monomer. When these compatible components are included in combination with low-profile additives and used in sheet molding compositions, articles with very smooth surfaces may be molded. Additionally, the flow of the sheet molding composition during the molding process is improved to the point that rapidly curing formulations may be composed. As a result, the molding time is drastically reduced.
The unsaturated polyester component of the four component resinous system comprises the polycondensation reaction product of one or more dihydric alcohols and one or more ethylenically unsaturated polycarboxylic acids. By polycarboxylic acid is generally meant the polycarboxylic or dicarboxylic acids or anhydrides, polycarboxylic or dicarboxylic acid halides, and polycarboxylic or dicarboxylic esters. Suitable unsaturated polycarboxylic acids, and the corresponding anhydrides and acid halides that contain polymerizable carbon-to-carbon double bonds may include maleic anhydride, maleic acid, and fumaric acid. A minor proportion of the unsaturated acid, up to about forty mole percent, may be replaced by dicarboxylic or polycarboxylic acid that does not contain a polymerizable carbon-to-carbon bond. Examples of which include O-phthalic, isophthalic, terephthalic, succinic, adipic, sebacic, methyl-succinic, and the like. Dihydric alcohols that are useful in preparing the polyesters include 1,2-propane diol (hereinafter referred to as propylene glycol), dipropylene glycol, diethylene glyco, 1,3-butanediol, ethylene glycol, glycerol, and the like. Examples of suitable unsaturated polyesters are the polycondensation products of (1) propylene glycol and maleic and/or fumaric acids; (2) 1,3-butanediol and maleic and/or fumaric acids; (3-combinations of ethylene and propylene glycols (approximately 50 mole percent or less of ethylene glycol) and maleic and/or fumaric acid; (4) propylene glycol, maleic and/or fumaric acids and dicyclopentadiene reacted with water. In addition to the above described polyesters one may also use dicyclopentadiene modified unsaturated polyester reins as described in the Pratt et al. U.S. Pat. No. 3,883,612. These examples are intended to be illustrative of suitable polyesters and are not intended to be all-inclusive. The acid number to which the polymerizable unsaturated polyesters are condensed is not particularly critical with respect to the ability of the low-profile resin to be cured to the desired product. Polyesters which have been condensed to acid numbers of less than 100 are generally useful, but acid numbers less than 70 are preferred. The molecular weight of the polymerizable unsaturated polyester may vary over a considerable range, but ordinarily those polyesters useful in the practice of the present invention have a molecular weight ranging from 300 to 5000, and more preferably, from about 500 to 5000.
In preferred embodiments, the unsaturated polyester is present in amounts ranging from about 20 to 45 percent, by weight, based on the total four component resinous system comprising the unsaturated polyester, the low-profile additive, monomer and compatible component. Especially preferred concentrations of the unsaturated polyester are in the 28 to 35 percent, by weight, range.
Low-profile additives are materials that when mixed in an unsaturated polyester and cured, result in a multiphase system. If the low-profile additive and the unsaturated polyester are compatible (from the standpoint that a gross phase separation does not take place) before cure, the system is known as a one-pack. Those mixtures which tend to separate into two or more layers on standing are known as a two-pack resin systems. This does, however, necessitate mixing immediately before use. Some polymers that are useful as low-profile additives include homopolymers and compolymers of acrylic and methacrylic acid esters, cellulose acetate butyrate, vinyl acetate homopolymers and copolymers, polyethylanes prepared from polyisocyanates, preferably diisocyanates, and polyether polyols, numerous saturated polyesters, polycaprolactone, styrenebutadiene copolymers, some modified celluloses, and certain alkyl oxide polymers. The above list of low-profile additives is not intended to list all low-profile additives but rather to show examples of materials which have been used to cause the multiphase morphology present in low profile resins. In preferred embodiments the thermoplastic additive is present in amounts ranging from 5 to 30 percent, by weight, based on the total four component resinous system. Especially preferred concentrations of thermoplastic additive are in the 7 to 20 percent, by weight range.
The monomer component of the resinous system comprises materials that copolymerize with the unsaturated polyester. The olefinically unsaturated monomer that is copolymerizible with the unsaturated polyester is most generally styrene, however, methyl-styrene is also useful. In preferred embodiments the monomer is present in amounts ranging from 25 to 65 percent, by weight, based on the total four component resinous system. Especially preferred concentrations of monomer are in the 35 to 50 percent, by weight range.
In the present invention one or more components are added which are compatible with the unsaturated polyester and monomer during the cure phase. That is, they do not act as low-profile additives. They do not cause a microphase separation during cure. According to the present invention, these compatible components give the added benefits of surface smoothness and better flowability, when compared with low-profile resin compositions without the compatible components. In the preferred embodiments the compatible component is present in amounts ranging from 0.5 to 15 percent, by weight, based on the total four component resinous sytem. Especially preferred concentrations of the compatible components are in the 1 to 8 percent, by weight range.
The compatible components of the present invention contain one or more oxyethane units, i.e., ##STR1## wherein R1, R2, R3, and R4, are selected from the group consisting of hydrogen, cycloalkyl, lower alkyl, phenyl, phenyl substituted by halogen, lower alkyl, acryl, or lower alkoxy; R1, R2, R3, and R4 may be the same or different; and a is an integer between about 1 and 200, and in some embodiments a is less than 100 and in certain embodiment a is less than 70.
The following terms used herein: "cycloalkyl", "lower alkyl", and "acyl" generally contain from 1 to 50 carbons, as is well understood by those skilled in the art.
One example of a compatible component is a compound containing one of more polyoxyethane substituents for the Formula I above wherein R1, R2, R3 and R4 are selected from the group consisting of H and lower alkyl; R1, R2, R3 and R4 may be the same or different; and, a is an integer between 1 and about 200, and in certain embodiments between 1 and about 70. Another example of a compatible component is wherein R1 =R2 =R3 =R4 =H, and a is an integer between 1 and 200, and in certain embodiments between 1 and about 70. Another example wherein R1 or R2 or R3 or R4 =CH3, and the others =H, and a is an integer between 1 and 200, and in certain embodiments between 1 and about 70.
It is desirable that the molecular weight of the compatible component is less than about 4000, the weight percent of the oxyethane unit described above is greater than or equal to 20, and the other atoms total is less than 240. In certain embodiments the compatible component wherein the molecular weight is less than about 3000; the weight percent of the oxyethane unit described above is greater than or equal to 20, and the other atoms total is less than about 200.
The molecular weight of the compatible compound is such that the compatible component remains compatible with the curing unsaturated polyester and monomer. Compatibility generally means that the combination of unsaturated polyester and low-profile additive do not cause the microporous phase separation widely accepted as necessary for the low-profile phenomenon. Low-profile additive components, by definition, are incompatible with the curing unsaturated polyester and monomer, and cause phase separation.
One example of compatible components that contain polyoxyethane substituents are polymers such as a polyalkylene oxide which has a molecular weight of between about 200-5000. The molecular weight of the polyalkylene oxide polymer is such that the compatible component remains compatible with the curing unsaturated polyester and monomer. When the molecular weight of the polymer is too high, the polyalkylene oxide polymer is incompatible with the curing unsaturated polyester and monomer. At that point the polyalkylene oxide polymer acts like a low-profile additive component, which by definition, is incompatible with the curing unsaturated polyester and monomer. Specific examples of polyalkylene oxide polymers useful as compatible components include polypropylene oxide having a molecular weight between about 200-1000 and polyethylene oxide having a molecular weight between about 200-5000.
Other examples of compatible components containing one or more polyoxyethane substituents are polyalkoxylated alkyl phenols such as polypropoxylated nonyl phenols, polyethoxylated nonyl phenols, polypropoxylated octyl phenols, polyethoxyated octyl phenols, and the like. Structure II below is an example of a polyalkoxylated alkyl phenol: ##STR2## wherein R5 is alkyl and R1, R2, R3, R4 and R6 are selected from the group consisting of hydrogen, cycloalkyl, lower alkyl, phenyl, phenyl substituted by halogen, lower alkyl, acyl, or lower alkoxy; R1, R2, R3, R4, R5 and R6 may be the same or different; and a is an integer between 1 and about 200.
Specific examples of alkoxylated alkyl phenols include wherein a =8-10, R1 =R2 =R3 =R4 =H, R5 =C8 H17 and R6 =H; and wherein a 8-10, and R1 or R2 or R3 or R4 =CH3 and the other =H, R5 =C8 H17 and R6 =H.
The following examples also illustrate that this oxyethane unit may be attached to numerous types of structures and be effective. An example of a compound that contains one of these oxyethane units is shown: ##STR3## wherein R1, R2, R3, R4 are selected from the group consisting of hydrogen, cycloalkyl, lower alkyl, phenyl, phenyl substituted by halogen, lower alkyl, acryl, or lower alkoxy; R5, and R6 are selected from the group consisting of hydrogen substituted benzyl, cycloalkyl, lower alkyl, phenyl, phenyl substituted by halogen, lower alkyl, acyl, or lower alkoxy, R1, R2, R3, R4, R5 and R6 maybe the same or different, and a is an integer between 1 and about 200.
Specific examples include:
Wherein R1 or R2 or R3 or R4 =CH3 and the others=H, R5 =CH3, and R6 is OCOCH3, a=2. This is dipropylene glycol monomethyl ether acetate.
Wherein R1 or R2 or R4 =CH3 and the other=H, R5 =CH3, and R6 is OH, a=2. This is dipropylene glycol monomethyl ether.
Wherein R1 or R2 or R3 or R4 =CH3 and the other=H, R5 =CH3, and R6 is OH, a=3. This is tripropylene glycol monomethyl ether.
Wherein R1, R2 R3 and R4 =H, R5 =CH3, and R6 =OH, a=2. This is diethylene glycol monomethyl ether.
In addition, the compatible components of the present invention include ethoxylated amines, such as for example, ##STR4## or mixtures of these wherein Z is the oxyethane unit, formula I above, R7 and R8 are hydrogen or a moiety containing between one and 25 carbon atoms, which may contain oxygen atoms, nitrogen atoms.
A specific type of amine is ##STR5## wherein R1, R2, R3, R4, and R7 are selected from the group consisting of hydrogen, cycloalkyl, lower alkyl, phenyl, phenyl substituted by halogen, lower alkyl, acyl, or lower alkoxy, R5, and R6 are selected from the group consisting of hydrogen, or hydrocarbon chains containing 8-22 carbons, or cycloalkyl, lower alkyl phenyl, phenyl substituted by halogen, lower alkyl, acyl, or lower alkoxy, and a is an integer between 1 and about 200, and R1, R2, R3, and R7, may be the same or different, and R5, and R6, may be the same or different.
Specific examples of ethoxylated amines are FIGS. VIA and VIB below: ##STR6## Wherein R1 =R2 =R3 =R4 =R5 =R7 =H, R6 =hydrocarbon chains containing 8-22 carbons.
Further, the compatible components of the present invention include monosaccharides that are partially esterified with carboxylic acid, and one or more of the remaining hydroxyls are ethoylated. For example: ##STR7## wherein one or more of R1, R2, R3, R4, R5, and R6 must be comprise the oxyethane group depicted in Formula I and the remainder must comprise hydrogen or ##STR8## (wherein R7 is cycloalkyl, alkyl up to 22 carbons, lower alkyl, phenyl, phenyl substituted by halogen, lower alkyl, or phenyl).
One example of such a monsaccharide comprises an ethoxylated sorbitan monooleate with about 5 ethylene oxide units.
An additional example is an ethoxylated sorbitan monooleate with about 20 ethylene oxide units.
Other examples that illustrate the applicability of this invention are listed in Table 1 below. These additives contain one or more polyoxyethane substituents as defined in Formula I.
The four component resinous system of this invention is suitable for mixing with other ingredients in order to form a sheet molding composition. For example, the four component resinous system is suitable for mixing with chemical thickeners which are physically mixed into the resin emulsion. The chemical thickeners generally include metal oxides, hydroxides and alkoxides of Group II, III or IV from the Periodic Table. Calcium oxide and magnesium oxide or the respective hydroxides are most often employed with four component resin compositions of the present invention. In preferred embodiments, the thickener is present in amounts ranging from about 0.5 to about 6 parts, by weight, based on the four component resinous system. The thickener is generally suspended in a carrier resin, as is known in the art. In preferred embodiments the carrier material comprises a composition which does not react with the thickener such as, for example, polymethylmethacrylate, polyvinylacetate, saturated or unsaturated polyesters, and similar materials well-known in the art. In preferred embodiments the carrier resin is present in amounts ranging from about 0.5 to about 8 parts, by weight based on one hundred parts of the four component resinous system.
Table II illustrates the preferred ranged for the four component mixture described in this invention.
Catalysts are incorporated in small amounts into thermosetting polyester resins containing ethylenically unsaturated monomer to aid in curing or cross-linking the unsaturated polyester with the monomer. Such catalysts are well known and may be similarly utilized in this invention to aid in curing the unsaturated polyester and monomer mixed with the low-profile thermoplastic polymer. Typical catalysts, for example, include organic peroxide and peracids such as tertiary butyl perbenzoate, tertiary butyl peroctoate, benzoyl peroxide and the like. The amounts of catalysts may be varied with the molding process and similarly varied with the level and types of inhibitors utilized, in a manner well known in the art. In preferred embodiments of the catalyst is present in amounts ranging from about 0.5 to about 2.5 parts, by weight, based on one hundred parts of the four component resinous system.
Curing of the composition is carried out under heat and pressure typically, in closed, preferably positive pressure type molds. Mold release agents may be added to the compositions to perform their normal function, as is well understood in the art. In preferred embodiments, the mold release agents are present in amounts ranging from about 0.5 to about 6.0 parts, by weight, based on one hundred parts of the four component resin system.
Fibers, fillers and pigments normally added to resin compositions can be likewise used in formulating the sheet molding composition of this invention. Reinforcing fibers or fibrous reinforcement is taken to mean glass fibers in one form or another, such as glass fabrics, chopped glass strands, chopped or continuous strand glass fiber mat; however, the terms also include reinforcing agents which may also be used if desired, for example, asbestos, cotton, synthetic organic fibers and metals. Fillers, usually inert, and inorganic material useful with the compositions of the present invention include, for example, clay, talc, calcium carbonate, silica, calcium silicate, and the like. In preferred embodiments the fillers are present in amounts ranging from about 165 to about 250 parts, by weight, based on one hundred parts of the four component resinous system.
Examples of pigments include carbon black, iron oxide, titanium dioxide, and the like, as well as organic pigments. In preferred embodiments the pigments are present in amounts ranging from about 0 to about 4 parts, by weight, based on one hundred parts of the four component resinous system.
In one aspect of the present invention the preparation of the sheet molding composition is generally carried out by blending together a first portion comprising the unsaturated polyester, the low-profile additive, the monomer, the compatible component, and such additives as a catalyst, mold release agent and fillers. This is generally known in the industry as the A-side formulation. The second portion (generally known as the B-side formulation) comprises the thickening agent and a carrier resin therefor, and such additives as pigments and mold release agents. In another aspect of the invention an additional or secondary monomer is added to the B-side formulation in which the thickener is suspended. In preferred embodiments the additional monomer comprises vinyl toluene or styrene. In preferred embodiments, the additional monomer is present in amounts ranging from about 1 to about 8 parts, by weight, based on one hundred parts of the four component resinous system.
The sheet molding composition of the present invention can be prepared by mixing the components in a suitable apparatus of temperatures which are conventional and known to those skilled in the art. Once the sheet molding composition is formulated, the composition can be molded into thermoset articles having a desired shape. The actual molding cycle will, of course, depend upon the exact composition being molded. In preferred embodiments suitable molding cycles are conducted at temperatures ranging from about 250°-350° F. for periods of time ranging from about 1/3 to about 5 minutes.
The following formulations are provided to illustrate examples of the compositions of the present invention and are not intended to restrict the scope thereof. All parts are parts by weight, unless otherwise expressly specified.
              TABLE II                                                    
______________________________________                                    
Resin Compositions                                                        
                            Preferred                                     
Ingredients    Range (wt. %)                                              
                            Range (wt. %)                                 
______________________________________                                    
Unsaturated polyester                                                     
               20-45        28-35                                         
Thermoplastic additive                                                    
                5-30         7-20                                         
(low-profile)                                                             
Monomer        25-65        35-50                                         
Compatible component                                                      
               0.5-15       1-8                                           
               100          100                                           
______________________________________
Various formulations using the sheet molding composition formulation shown in Table III below were made.
              TABLE III                                                   
______________________________________                                    
Typical Sheet Molding Composition Formulation                             
Ingredients      Amount                                                   
______________________________________                                    
Resin            100                                                      
Catalyst         1.4                                                      
Release agent    4.2                                                      
Filler           215                                                      
Thickener        3.7                                                      
Pigment          0.2                                                      
Carrier          1.9                                                      
Secondary monomer                                                         
                 3.7                                                      
______________________________________
In addition, the remaining ingredients were the same for each formulation: the unsaturated polyester comprises maleic anhydride and propylene glycol; the low-profile additive comprises a saturated polyester made from ethylene glycol and propylene glycol and adipic acid; the monomer comprises styrene; the compatible components are listed in Table I; the catalyst comprises tertiary butyl perbenzoate; the release agent comprises calcium stearate and zinc stearate; the filler comprises calcium carbonate; the thickener comprises magnesium hydroxide; the carrier comprising polymethylmethacrylate; the pigment comprises a carbon black pigment suspension; and the secondary monomer comprises vinyl toluene.
Compression molded panels were made with each formulation with 27 percent, by weight, of 1" chopped glass fibers. When measured on a surface smoothness index instrument (LORIA® registered trademark of the Ashland Chemical Co.) the panels gave the LORIA® number as listed in Table I below as compared to the same formulation but without any compatible component, which gave a number of 80-90. On the LORIA® instrument, the lower the number, the smoother the surface. The additives listed in Table I below contain the oxyethylene unit, as described in this invention. It is within the contemplated scope of the present invention that the compatible components especially useful in the four component resinous system have a surface smoothness value within the ranges set forth in Table I below. In preferred embodiments, it is contemplated that the surface smoothness values of the four component resinous systems containing compatible components, be about 50 or less, as measured using a LORIA® surface smoothness index instrument.
              TABLE 1                                                     
______________________________________                                    
                  COMMON OR                                               
COMPATIBLE COMPONENT                                                      
                  TRADENAME     LORIA                                     
______________________________________                                    
Polypropylene glycol ceteareth-9                                          
                  Eumulgin L    61                                        
Polyoxyethane-co-polyoxy-                                                 
                  Genapol PN-30 57                                        
propane amine                                                             
Polyalkoxylated quaternary                                                
                  Cirrasol G-250                                          
                                56                                        
amine                                                                     
Polyoxypropane (10) cetyl                                                 
                  Crodafos CAP  81.5                                      
ether phosphate                                                           
Sodium alkylaminopolyethoxy-                                              
                  Triton QS-15  60                                        
ethyl sulfate                                                             
Polyoxyethylated (5) Oleic Acid                                           
                  Emulphor VN-430                                         
                                44                                        
Polyoxyethylated (30) Caster Oil                                          
                  Emulphor EL-620                                         
                                41                                        
Polyoxyethylated (20) Oleyl                                               
                  Emulphor ON-870                                         
                                43.5                                      
Alcohol                                                                   
Ethoxylated Mono and                                                      
                  Durfax EOM K  57                                        
Diglycerides                                                              
Polypropoxylated (6) Phenol                                               
                  POP (6) Phenol                                          
                                50                                        
Ethoxylated Aromatic Alcohol                                              
                  Mazon JMR-1   66                                        
Phosphate                                                                 
Ethoxylated-Propoxylated Linear                                           
                  Rexonic P-1   62                                        
Alcohol                                                                   
Phosphated Alkylphenol                                                    
                  Rexophos 25/97                                          
                                76                                        
Ethoxylate                                                                
88% Dimethyl Polyethylene                                                 
                  Dow Corning   69                                        
Glycol 12% Acetate Silicone                                               
                  FF-400                                                  
Copolymers                                                                
88% Polyoxyethyleneglycol                                                 
                  Dow Corning 193                                         
                                42                                        
Silicone Copolymer                                                        
12% Allyl Alcohol Ethoxylated                                             
Aromatic Alcohol (ethoxylated)                                            
                  Maphos JM-71  80                                        
Phosphate                                                                 
Ethoxylated Linear Alcohol                                                
                  Alfonic 1012-40                                         
                                49                                        
(40% E.O.)                                                                
Polyethoxylated (20) Glyceryl                                             
                  Aldosperse    42                                        
Stearate          MS-20-PG                                                
Polyethoxylated (10) Cetyl Ether                                          
                  BRIJ 56       48                                        
Ethoxylated (20) Methyl                                                   
                  Glucamate SSE-20                                        
                                45                                        
Glucoside Sesquisterate                                                   
Carboxylated Ethoxylated                                                  
                  Emcol CBA-60  53                                        
Alcohol                                                                   
Polyethoxylated lauramide MEA                                             
                  Mazamide L-5  42                                        
Ethoxylated Hydrogenated                                                  
                  Lipolan 31    50                                        
Lanolin                                                                   
Propylene Glycol Sterate                                                  
                  Lipo PGMS     60                                        
Alcohols (C-10 to C-16)                                                   
                  AE-3          44                                        
Ethoxylated                                                               
Alcohols (C-10 to C-16)                                                   
                  AE-7          46                                        
Ethoxylated                                                               
Carboxylated Ethoxylated                                                  
                  Emcol CBA-60  53                                        
Alcohol                                                                   
Polyethoxylated (20) Oleyl                                                
                  ON870         44                                        
Alcohol                                                                   
Propylene Glycol Hydroxy                                                  
                  Naturechem PGHS                                         
                                53                                        
Sterate                                                                   
EO/PO Type Surfactant                                                     
                  Pluronic L-35 52                                        
EO/PO Surfactant  Pluronic L-64 58.2                                      
EO Adducts Of Polypropylene                                               
                  Union Carbide 77                                        
Triola (25% polymer-30/70                                                 
                  E-564                                                   
Acrylonitrile-Styrene)                                                    
Polyalkyleneoxidemethylsiloxane                                           
                  Union Carbide 50                                        
Copolymer         L-562                                                   
Polyethoxylated (6) Bisphenol A                                           
                  POE 6 Bisphenol A                                       
                                58                                        
Polypropoxylated (6)                                                      
                  POP 6 -2Ethyl 54                                        
2-Ethylhexanol    hexanol                                                 
Polypropoxylated (6)                                                      
                  POP 6 Nonylphenol                                       
                                55                                        
Nonylphenol                                                               
EO/PO Surfactant  Pluronic L-63 61                                        
Polyoxyethylene (5) Sorbitan                                              
                  Glycosperse O-5                                         
                                56                                        
Monooleate                                                                
Polyethoxylated (20)                                                      
                  Flo Mo SMO-20 58                                        
Sorbitan Monooleate                                                       
Polyethylene Glycol M.W. 600                                              
                  Polyethyleneglycol                                      
                                47                                        
                  MW 600                                                  
Polyethylene Glycol Mono-                                                 
                  PEGME         53                                        
methylether                                                               
Polyethoxylated (5) Tallow                                                
                  TAM-5         58                                        
Amine                                                                     
Polyethoxylated (20) Sorbitan                                             
                  Tween 80      56.2                                      
Monooleate                                                                
Polyethoxylated (5) Sorbitan                                              
                  Tween 81      55                                        
Monooleate                                                                
Nonylphenoxy Polyethoxy                                                   
                  Triton N-57   52.9                                      
Ethanol                                                                   
Octylphenoxy Polyethoxy                                                   
                  Triton X-15   53.8                                      
Ethanol                                                                   
Polyoxyethylated (8)                                                      
                  Ethox MA-8    45                                        
Monomerate                                                                
Polyoxyethylated (9) Tallate                                              
                  Ethox TO-9A   45                                        
Polyoxyethylene Decyl Phos-                                               
                  Ethfac 361    61                                        
phate Potassium Salt                                                      
Polyethoxylated (5) Laurate                                               
                  Ethox ML-5    45                                        
Polyethoxylated (9) Laurate                                               
                  Ethox ML-9    45                                        
Polyethoxylated (14) Laurate                                              
                  Ethox ML-14   46                                        
Polyethoxylated (9) Isostearate                                           
                  Ethox MI-9    51                                        
Polyethoxylated (14) Isostearate                                          
                  Ethox MI-14   48                                        
Polyethoxylated (9) Oleate                                                
                  Ethox MO-9    51                                        
Polyethoxylated (14) Oleate                                               
                  Ethox MO-14   44                                        
Polyethoxylated Nonylphenol                                               
                  Gedepal CO 210                                          
                                59                                        
Polyethoxylated Nonylphenol                                               
                  Alaksurf NP-15                                          
                                47                                        
Ethoxylated Octyl Phenol                                                  
                  Triton X-45   59                                        
Ethoxylated Octylphenol                                                   
                  Triton X-102  53                                        
Polyoxyethane (15) Cocoamine                                              
                  CAM-15        54                                        
Dipropyleneglycol Mono-                                                   
                  DPGMME        50                                        
methylether                                                               
______________________________________
In addition, the sheet molding compositions of the above formulations have shown unexpected improvements in surface aesthetics and mold fillout. These improvements are especially significant for use in sheet molding compound (SMC). Moreover, increasingly thinner automobile parts are able to be molded with smoother surfaces than by any known systems.
Although the invention has been described in its preferred form with a certain degree of particularity, it is understood that the present disclosure has been made only by way of example, and that numerous changes can be made without departing from the spirit of the scope of the invention.

Claims (21)

We claim:
1. A four component resinous system for a sheet molding composition comprising:
(a) an unsaturated polyester comprising a polycondensation product of one or more dihydric alcohols and one or more ethylenically unsaturated polycarboxylic acids;
(b) one or more low-profile thermoplastic polymers which cause phase separation and porosity during a curing reaction;
(c) one or more olefinically unsaturated monomers which copolymerizes with the unsaturated polyester, and,
(d) one or more components which remain compatible during cure of the unsaturated polyester and monomer, wherein the compatible component is selected from the group of compounds containing one or more polyoxyethane substituents having a general structure ##STR9## wherein R1, R2, R3 and R4 are selected from the group consisting of hydrogen, cycloalkyl, lower alkyl, phenyl, phenyl substituted by halogen, lower alkyl, acyl or lower alkoxy; R1, R2, R3 and R4 may be the same or different; and a is an integer between 1 and about 200.
2. The composition of claim 1, wherein the compatible component is selected from the group of compounds containing one or more polyoxyethane substituents having a general structure: ##STR10## wherein R1, R2, R3 and R4 are selected from the group consisting of hydrogen or lower alkyl; R1, R2, R3 and R4 may be the same or different; and a is an integer between 1 and about 200.
3. The composition of claim 1, wherein the compatible component is selected from the group of compounds containing one or more polyoxyethane substituents having a general structure: ##STR11## wherein R1, R2, R3, and R4 =H; and a is an integer between 1 and about 200.
4. The composition of claim 1, wherein the compatible component is selected from the group of compounds containing one or more polyoxyethane substituents having a general structure; ##STR12## wherein R1 or, R2 or, R3 or, R4 =CH3 and the others=H; and a is an integer between 1 and 200.
5. The composition of claim 1, wherein the compatible component has a molecular weight less than about 4000, wherein the polyoxyethane substituents comprise greater than or equal to 20% of said molecular weight and the molecular weight of the atoms of the compatible component, exclusive of the polyoxyethane substituents, totals less than about 240.
6. The composition of claim 2, wherein the compatible component has a molecular weight less than about 4000, wherein the polyoxyethane substituents comprise greater than or equal to 20% of said molecular weight and the molecular weight of the atoms of the compatible component, exclusive of the polyoxyethane substituents totals less than about 240.
7. The composition of claim 3, wherein the compatible component has a molecular weight less than about 4000, wherein the polyoxyethane substituents comprise greater than or equal to 20% of said molecular weight and the molecular weight of the atoms of the compatible component, exclusive of the polyoxyethane substituents, totals less than about 240.
8. The composition of claim 4, wherein the compatible component has a molecular weight less than about 4000, wherein the polyoxyethane substituents comprise greater than or equal to 20% of said molecular weight and the molecular weight of the atoms in the compatible component, exclusive of the polyoxyethane substituents, totals less than about 240.
9. The composition of claim 1, wherein the compatible component has a molecular weight less than about 3000, wherein the polyoxyethane substituents comprise greater than or equal to 20% of said molecular weight and the molecular weight of the atoms in the compatible component, exclusive of the polyoxyethane substituents, totals less than about 200.
10. The composition of claim 2, wherein the compatible component has a molecular weight less than about 3000, wherein the polyoxyethane substituents comprise greater than or equal to 20% of said molecular weight and the molecular weight of the atoms in the compatible component, exclusive of the polyoxyethane substituents, totals less than about 200.
11. The composition of claim 3, wherein the compatible component has a molecular weight less than about 3000, wherein the polyoxyethane substituents comprise greater than or equal to 20% of said molecular weight and the molecular weight of the atoms in the compatible component, exclusive of the polyoxyethane substituents, totals less than about 200.
12. The composition of claim 4, wherein the compatible component has a molecular weight less than about 3000, wherein the polyoxyethane substituents comprise greater than or equal to 20% of said molecular weight and the molecular weight of the atoms in the compatible component, exclusive of the polyoxyethane substituents, totals less than about 200.
13. The composition of claim 1, wherein the compatible component has a molecular weight of between about 200-5000.
14. The composition of claim 1, wherein the compatible component is selected from the group consisting of polyethoxylated (5) oleic acid, polyethoxylated (30) caster oil, polyethoxylated nonylphenol ether phosphate, polyethoxylated (20) oleyl alcohol, polypropoxylated (6) phenol, 88% polyoxyetheneglycol silicone copolymer 12% allyl alcohol ethoxylated, ethoxylated linear alcohol (40% E.O.), polyoxyethylene (20) glycerol stearate, polyoxyethylene (10) cetyl ether, polyethoxylated (20) methyl glucoside sesquisterate, polyethoxylated (6) lauramide MEA, ethoxylated hydrogenated lanolin, alcohols (C-10 to C-16) ethoxylated, polyethoxylated (20) oleyl alcohol, polyalkyleneoxidedimethylsiloxane copolymer, polyethylene glycol M.W. 600, polyethoxylated (8) monomerate, polyethoxylated (9) tallate, poyethoxylated (5) laurate, polyethoxylated (9) laurate, polyethoxylated (14) laurate, polyethoxylated (14) isostearate, polyethoxylated (14) oleate, polyethoxylated nonylphenol, and dipropyleneglycol monomethylether.
15. The composition of claim 1, wherein the compatible component has a surface smoothness value of about 50 or less.
16. The composition of claim 1, wherein the unsaturated polyester comprises the polycondensation product of dihydric alcohols and an ethylenically unsaturated polycarboxylic acid.
17. The composition of claim 7, wherein the unsaturated polyester is selected from the group consisting essentially of a polycondensation product of maleic and/or fumaric acids and propylene glycol; the polycondensation product of 1,3-butanediol and maleic and/or fumaric acids; the polycondensation product of ethylene and propylene glycols comprising approximately 50 mole percent or less of ethylene glycol, and maleic and/or fumaric acids; the polycondensation product of propylene glycol, maleic and/or fumaric acids and dicyclopentadiene reacted with water; and the polycondensation product of propylene glycol, maleic and/or fumaric acids and isophthalic acid.
18. The composition of claim 1, wherein the low-profile thermoplastic polymer is selected from the group consisting essentially of a reaction product of ethylene glycol and propylene glycol and adipic acid; a polyvinyl acetate homopolymer or copolymer; and a polymethylmethacrylate.
19. The composition of claim 1, wherein the monomer is selected from the group consisting essentially of styrene, methyl-styrene, and vinyl toluene.
20. The composition of claim 1, wherein the unsaturated polyester is present in an amount of approximately 25-45 percent, the low-profile thermoplastic polymer is present in an amount of approximately 5-30 percent, the monomer is present in an amount of approximately 25-65 percent and, the compatible component is present in an amount of approximately 0.5-15 percent, by weight, of the four component resin.
21. The composition of claim 11, wherein the unsaturated polyester is present in an amount of approximately 28-35 percent, the low-profile thermoplastic polymer is present in an amount of approximately 7-20 percent, the monomer is present in an amount of approximately 35-50 percent and, the compatible component is present in an amount of approximately 1-8 percent, by weight, of the four component resin.
US07/517,775 1989-10-30 1990-05-02 Unsaturated polyester resin compositions containing compatible compounds Expired - Lifetime US5162401A (en)

Priority Applications (14)

Application Number Priority Date Filing Date Title
US07/517,775 US5162401A (en) 1989-10-30 1990-05-02 Unsaturated polyester resin compositions containing compatible compounds
EP90916979A EP0451258B1 (en) 1989-10-30 1990-10-01 Unsaturated polyester resin compositions containing compatible compounds
CA002026636A CA2026636A1 (en) 1989-10-30 1990-10-01 Unsaturated polyester resin compositions containing compatible compounds
BR909006979A BR9006979A (en) 1989-10-30 1990-10-01 UNSATURATED POLYESTER RESIN COMPOSITES CONTAINING COMPATIBLE COMPOUNDS
ES90916979T ES2113863T3 (en) 1989-10-30 1990-10-01 COMPOSITIONS OF UNSATURATED POLYESTER RESINS CONTAINING COMPATIBLE COMPOUNDS.
PCT/US1990/005541 WO1991006604A1 (en) 1989-10-30 1990-10-01 Unsaturated polyester resin compositions containing compatible compounds
DE69031800T DE69031800D1 (en) 1989-10-30 1990-10-01 UNSATURATED POLYESTER RESIN COMPOSITIONS COMPATIBLE MEASURES
JP2515512A JPH04502645A (en) 1989-10-30 1990-10-01 Unsaturated polyester resin composition containing compatible compounds
AU67300/90A AU6730090A (en) 1989-10-30 1990-10-01 Unsaturated polyester resin compositions containing compatible compounds
KR1019910700668A KR920701357A (en) 1989-10-30 1990-10-01 Unsaturated polyester resin composition containing a miscible compound
DK90916979T DK0451258T3 (en) 1989-10-30 1990-10-01 Unsaturated Polyester Resin Compositions Containing Compatible Compounds
CN90108700A CN1030713C (en) 1989-10-30 1990-10-29 Unsaturated polyester resin compositions containing compatible compounds
NO91912465A NO912465L (en) 1989-10-30 1991-06-24 UNSATURED POLYESTER RESIN COMPOSITIONS CONTAINING COMPATIBLE COMPOUNDS.
FI913164A FI913164A0 (en) 1989-10-30 1991-06-28 OMAETTADE POLYESTERHARTSKOMPOSITIONER INNEHAOLLANDE KOMBINERBARA FOERENINGAR.

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US07/428,548 US5089544A (en) 1989-10-30 1989-10-30 Unsaturated polyester resin compositions containing compatible compounds
US07/517,775 US5162401A (en) 1989-10-30 1990-05-02 Unsaturated polyester resin compositions containing compatible compounds

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5393849A (en) * 1993-10-19 1995-02-28 Georgia-Pacific Resins, Inc. Curable polyester/polyamino compositions
EP0700948A2 (en) 1994-09-09 1996-03-13 Owens-Corning Fiberglas Corporation Low-profile additive for unsaturated polyesters
EP0737229A1 (en) * 1993-11-12 1996-10-16 Ashland Oil, Inc. Enhancers for thermoplastic low profile additives
US5883166A (en) * 1997-06-26 1999-03-16 Jennings; Thomas C. Liquid internal mold release agents for unsaturated polyester thermosetting molding compounds
US5900311A (en) * 1994-03-23 1999-05-04 Cook Composites And Polymers Co. Thermosetting polyester composites prepared via vacuum-assisted technique with smooth surface appearance
US6001919A (en) * 1998-04-06 1999-12-14 The Budd Company Conductive sheet molding compound
US20080154002A1 (en) * 2006-12-22 2008-06-26 Reichhold, Inc. Molding resins using renewable resource component
US20090105406A1 (en) * 2006-04-27 2009-04-23 Wacker Chemie Ag Use of functionalized polyvinyl esters for increasing the surface tension of bmc/smc parts
US10246584B2 (en) * 2014-12-09 2019-04-02 Lubrizol Advanced Materials, Inc. Additive to prevent phase separation of low profile additive in unsaturated thermoset polyester compositions
EP3626759A1 (en) * 2018-09-21 2020-03-25 Erfindergemeinschaft Lorenz + Grahneis GbR High-temperature-up-resins (ht-up resin) based on cyclic and non-cyclic raw materials (ht-up)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0598227A1 (en) * 1992-10-19 1994-05-25 Takeda Chemical Industries, Ltd. Low-pressure and low-temperature moldable composition and shaped article therefrom
UA27979C2 (en) * 1995-10-20 2000-10-16 Роман Олександрович Веселовський An oligoether composition for protective coatings, which is polymerized, a method for application of protective coatings on surfaces of metal articles and a mechanism for realizing the method
US5880180A (en) * 1997-09-26 1999-03-09 Ashland Inc. Aldimine surface quality enhancers
CA2325972A1 (en) 1999-11-24 2001-05-24 Dainippon Ink And Chemicals, Inc. Compatibilizing agent, radical copolymerizable unsaturated resin composition, molding material, and molded article
CN101255267B (en) * 2008-04-14 2011-05-11 上纬（上海）精细化工有限公司 Saturated polyester resin type low-contour additive
NL2005685C2 (en) * 2010-11-12 2012-05-15 Visker Beheer B V COATING SYSTEM, APPLICATION THEREOF, AND METHOD FOR MANUFACTURING THEM.
PL3387094T3 (en) * 2015-12-10 2022-01-31 Ecolab Usa Inc. Abrasion-masking composition for use with reusable containers and the method of using the same
CN109627705B (en) * 2018-11-28 2020-11-10 宁波力达得为高分子科技有限公司 Acid and alkali resistant chemically modified PET composite material and preparation method thereof

Citations (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3549586A (en) * 1969-04-01 1970-12-22 Union Carbide Corp Polyester compositions
US3650997A (en) * 1970-08-13 1972-03-21 Immont Corp Coating compositions containing epoxy resins and carboxyl terminated polyesters
US3652502A (en) * 1970-08-05 1972-03-28 Eastman Kodak Co Linear polyesters having free carboxyl radicals distributed along the molecular chain coatings thereof and coated substrates
US3701748A (en) * 1966-07-20 1972-10-31 Rohm & Haas Unsaturated polyester resinous compositions
US3772241A (en) * 1966-07-20 1973-11-13 Rohm & Haas Unsaturated polyester resinous compositions
US3833411A (en) * 1971-10-18 1974-09-03 Bell Telephone Labor Inc Articles coated with alkali-soluble polyester-type resins and method of producing them
US3883612A (en) * 1971-06-07 1975-05-13 Scm Corp Low-shrink thermosetting polymers
US3931438A (en) * 1971-11-08 1976-01-06 Corning Glass Works Differential densification strengthening of glass-ceramics
US3931422A (en) * 1974-10-04 1976-01-06 Standard Oil Company Polyester/starch paper sizing
US4100229A (en) * 1976-03-11 1978-07-11 Hooker Chemicals & Plastics Corp. Low profile additives in polyester systems
US4160758A (en) * 1978-01-30 1979-07-10 Exxon Research & Engineering Co. Method of manufacture of elastomer polyester molding compounds
US4263199A (en) * 1979-11-13 1981-04-21 Union Carbide Corporation Polyester molding compositions
US4275189A (en) * 1980-02-28 1981-06-23 Cargill, Incorporated Neopentyl glycol, terephthalate, dicarboxy acid, trimellitate thermosetting resin
US4288571A (en) * 1971-01-18 1981-09-08 Union Carbide Corporation Polyester compositions
US4293686A (en) * 1980-04-18 1981-10-06 Union Carbide Corporation Thermosetting polyester resin composition
US4374215A (en) * 1979-11-13 1983-02-15 Union Carbide Corporation Polyester moldings
EP0075765A1 (en) * 1981-09-11 1983-04-06 Union Carbide Corporation Polyester molding compositions
US4387211A (en) * 1980-12-26 1983-06-07 Kao Soap Co., Ltd. Process for producing new polyester resin and product thereof
US4446301A (en) * 1983-08-03 1984-05-01 Eastman Kodak Company Modified polyesters
US4459401A (en) * 1983-05-04 1984-07-10 Desoto, Inc. Polyester oligomer and high solids thermosetting coatings
US4473544A (en) * 1979-11-24 1984-09-25 Machulla Hans Juergen Radio-iodine-labelled omega phenyl fatty acids
US4525498A (en) * 1980-10-16 1985-06-25 Union Carbide Corporation Polyester fiber reinforced molding compounds
US4525524A (en) * 1984-04-16 1985-06-25 The Goodyear Tire & Rubber Company Polyester composition
US4555534A (en) * 1981-03-26 1985-11-26 Union Carbide Corporation Uniformly pigmented, low shrinking polyester molding compositions
US4622354A (en) * 1985-10-22 1986-11-11 The Budd Company Phase stabilized polyester molding material
US4735995A (en) * 1987-03-27 1988-04-05 The Sherwin-Williams Company Water reducible acrylic modified polyester compositions
US4787989A (en) * 1988-01-13 1988-11-29 Gaf Corporation Anionic soil release compositions
EP0335406A2 (en) * 1988-03-31 1989-10-04 Union Carbide Corporation Low profile molding system

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2531092B1 (en) * 1982-07-27 1985-10-11 Ugine Kuhlmann ANTI-SHRINKAGE ADDITIVE FOR AN UNSATURATED POLYESTER, A METHOD FOR PRODUCING THE SAME, ANTI-SHRINKAGE COMPOSITION
JPS6420219A (en) * 1987-07-15 1989-01-24 Kanegafuchi Chemical Ind Unsaturated polyester resin composition and laminate for electrical use
NL8701932A (en) * 1987-08-18 1989-03-16 Dsm Resins Bv THERMO-HARDBAR COMPOSITION.

Patent Citations (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3701748A (en) * 1966-07-20 1972-10-31 Rohm & Haas Unsaturated polyester resinous compositions
US3772241A (en) * 1966-07-20 1973-11-13 Rohm & Haas Unsaturated polyester resinous compositions
US3549586A (en) * 1969-04-01 1970-12-22 Union Carbide Corp Polyester compositions
US3652502A (en) * 1970-08-05 1972-03-28 Eastman Kodak Co Linear polyesters having free carboxyl radicals distributed along the molecular chain coatings thereof and coated substrates
US3650997A (en) * 1970-08-13 1972-03-21 Immont Corp Coating compositions containing epoxy resins and carboxyl terminated polyesters
US4288571A (en) * 1971-01-18 1981-09-08 Union Carbide Corporation Polyester compositions
US3883612A (en) * 1971-06-07 1975-05-13 Scm Corp Low-shrink thermosetting polymers
US3833411A (en) * 1971-10-18 1974-09-03 Bell Telephone Labor Inc Articles coated with alkali-soluble polyester-type resins and method of producing them
US3931438A (en) * 1971-11-08 1976-01-06 Corning Glass Works Differential densification strengthening of glass-ceramics
US3931422A (en) * 1974-10-04 1976-01-06 Standard Oil Company Polyester/starch paper sizing
US4100229A (en) * 1976-03-11 1978-07-11 Hooker Chemicals & Plastics Corp. Low profile additives in polyester systems
US4160758A (en) * 1978-01-30 1979-07-10 Exxon Research & Engineering Co. Method of manufacture of elastomer polyester molding compounds
US4263199A (en) * 1979-11-13 1981-04-21 Union Carbide Corporation Polyester molding compositions
US4374215A (en) * 1979-11-13 1983-02-15 Union Carbide Corporation Polyester moldings
US4473544A (en) * 1979-11-24 1984-09-25 Machulla Hans Juergen Radio-iodine-labelled omega phenyl fatty acids
US4275189A (en) * 1980-02-28 1981-06-23 Cargill, Incorporated Neopentyl glycol, terephthalate, dicarboxy acid, trimellitate thermosetting resin
US4293686A (en) * 1980-04-18 1981-10-06 Union Carbide Corporation Thermosetting polyester resin composition
US4525498A (en) * 1980-10-16 1985-06-25 Union Carbide Corporation Polyester fiber reinforced molding compounds
US4387211A (en) * 1980-12-26 1983-06-07 Kao Soap Co., Ltd. Process for producing new polyester resin and product thereof
US4555534A (en) * 1981-03-26 1985-11-26 Union Carbide Corporation Uniformly pigmented, low shrinking polyester molding compositions
EP0075765A1 (en) * 1981-09-11 1983-04-06 Union Carbide Corporation Polyester molding compositions
US4459401A (en) * 1983-05-04 1984-07-10 Desoto, Inc. Polyester oligomer and high solids thermosetting coatings
US4446301A (en) * 1983-08-03 1984-05-01 Eastman Kodak Company Modified polyesters
US4525524A (en) * 1984-04-16 1985-06-25 The Goodyear Tire & Rubber Company Polyester composition
US4622354A (en) * 1985-10-22 1986-11-11 The Budd Company Phase stabilized polyester molding material
US4735995A (en) * 1987-03-27 1988-04-05 The Sherwin-Williams Company Water reducible acrylic modified polyester compositions
US4787989A (en) * 1988-01-13 1988-11-29 Gaf Corporation Anionic soil release compositions
EP0335406A2 (en) * 1988-03-31 1989-10-04 Union Carbide Corporation Low profile molding system

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
STN International Search Results Abstract relates to the European Application No. 335406. *

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5393849A (en) * 1993-10-19 1995-02-28 Georgia-Pacific Resins, Inc. Curable polyester/polyamino compositions
EP0737229A1 (en) * 1993-11-12 1996-10-16 Ashland Oil, Inc. Enhancers for thermoplastic low profile additives
EP0737229A4 (en) * 1993-11-12 1997-09-03 Ashland Oil Inc Enhancers for thermoplastic low profile additives
US5900311A (en) * 1994-03-23 1999-05-04 Cook Composites And Polymers Co. Thermosetting polyester composites prepared via vacuum-assisted technique with smooth surface appearance
EP0700948A2 (en) 1994-09-09 1996-03-13 Owens-Corning Fiberglas Corporation Low-profile additive for unsaturated polyesters
US5883166A (en) * 1997-06-26 1999-03-16 Jennings; Thomas C. Liquid internal mold release agents for unsaturated polyester thermosetting molding compounds
US6001919A (en) * 1998-04-06 1999-12-14 The Budd Company Conductive sheet molding compound
US20090105406A1 (en) * 2006-04-27 2009-04-23 Wacker Chemie Ag Use of functionalized polyvinyl esters for increasing the surface tension of bmc/smc parts
US20080154002A1 (en) * 2006-12-22 2008-06-26 Reichhold, Inc. Molding resins using renewable resource component
US7985826B2 (en) * 2006-12-22 2011-07-26 Reichhold, Inc. Molding resins using renewable resource component
US8110650B2 (en) 2006-12-22 2012-02-07 Reichold, Inc. Methods for making molding resins
US10246584B2 (en) * 2014-12-09 2019-04-02 Lubrizol Advanced Materials, Inc. Additive to prevent phase separation of low profile additive in unsaturated thermoset polyester compositions
EP3626759A1 (en) * 2018-09-21 2020-03-25 Erfindergemeinschaft Lorenz + Grahneis GbR High-temperature-up-resins (ht-up resin) based on cyclic and non-cyclic raw materials (ht-up)
WO2020058460A1 (en) * 2018-09-21 2020-03-26 Erfindergemeinschaft Lorenz + Grahneis Gbr High-temperature-up-resins (ht-up resin) based on cyclic and non-cyclic raw materials (ht-up)

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FI913164A0 (en) 1991-06-28
EP0451258B1 (en) 1997-12-10
ES2113863T3 (en) 1998-05-16
DK0451258T3 (en) 1998-08-24
CN1030713C (en) 1996-01-17
NO912465D0 (en) 1991-06-24
AU6730090A (en) 1991-05-31
JPH04502645A (en) 1992-05-14
WO1991006604A1 (en) 1991-05-16
CN1052490A (en) 1991-06-26
EP0451258A1 (en) 1991-10-16
NO912465L (en) 1991-06-24
BR9006979A (en) 1991-12-24
CA2026636A1 (en) 1991-05-01
KR920701357A (en) 1992-08-11

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